JP2953300B2 - Sterilization method of water containing reducing substances - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel industrial germicide. More specifically, the present invention relates to an industrial germicide that exhibits an excellent bactericidal effect stably over a long period of time even in an aqueous system containing a reducing substance.

[0002]

2. Description of the Related Art In a raw material preparation step and a paper making step in the papermaking industry, bacteria and fungi are propagated using cellulose and various additives as nutrients to generate slime.
When such slime is peeled off from the wall surface, it is mixed as a foreign substance in the product, and lowers the product quality or induces paper breakage in the paper making process, hinders continuous operation, and undesirably reduces production efficiency. Invite the situation.
In the papermaking process, rosin-based sizing agents, starch, gelatin, latex, casein, and the like are used in large amounts as additives, and since these additives are all nutrient sources, microorganisms are in a state where they can easily propagate. . 2. Description of the Related Art Conventionally, in various industrial fields, treatment with a bactericide has been performed for microbial disorders such as bacteria and fungi because its implementation is relatively simple and economical. However, in a system in which a reducing substance such as a sulfite ion or a thiosulfate ion is present, the efficacy of the conventional antibacterial agent or bactericide is significantly reduced, and the stable operation is hindered. Further, in a system in which decay such as starch or latex is progressing, a reducing substance such as hydrogen sulfide is generated, and it has been a serious problem that the effectiveness of the conventional preservative is significantly inhibited. As a sterilization method in the presence of such a reducing substance, a method of oxidatively decomposing the reducing substance with a chlorine-based chemical or the like and then using a conventional sterilizing agent has been used. However, in the papermaking process, the concentration of the reducing substance in the system fluctuates with time, so that it has been difficult to always decompose properly and stably. Therefore, when a conventional disinfectant is used in such a papermaking process, a large amount of the disinfectant must be added at a concentration higher than the reducing substance concentration, which is economically unreasonable. Therefore, at present, the situation has to be dealt with by frequently cleaning the inside of the system.

[0003]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an industrial germicide which exhibits a stable and excellent bactericidal effect even in a system containing a reducing substance. It was made for the purpose.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an industrial germicide which exhibits a specific bactericidal effect even in a system in which the above-mentioned reducing substance is present. It has been found that the object can be achieved by combining 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane or 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane with a specific compound. Based on the above, the present invention has been completed. That is, the present invention relates to the following: (1) Sulfite ion, thiosulfate ion or hydrogen sulfide
The inclusion compound of 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and an isothiazolin-3-one compound and a brominated acetic acid ester in an aqueous system of ppm or more are mixed in a weight ratio of 1:20 to 20: 1. (2) When used in an aqueous system as a slime control agent in a papermaking process, wherein the total amount of active ingredients is 0.1 to 100.
g / m ^3. (1)
(3) A method for disinfecting water containing a reducing substance according to item (3), which is used in an aqueous system as a preservative, and is added so that the total amount of active ingredients is 1 to 2000 g / m ^3. (1) A method for sterilizing water containing a reducing substance according to the above (1).

Hereinafter, the present invention will be described in detail. 2,2'-dihydroxy-5, used in the fungicide of the present invention
5'-dichlorodiphenylmethane is a compound represented by the formula [1].

Embedded image There are various industrial fungicides used for aqueous systems, and examples thereof include thiocyanate compounds, halocyanoacetamide compounds, isothiazolone compounds, dithiocarbamic acid compounds, and benzylammonium chloride compounds. . However, although these industrial disinfectants all have considerable effects in ordinary aqueous systems, their efficacy is extremely reduced when aqueous systems contain reducing substances, and they have little practical use. On the other hand, 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane used in the aqueous disinfectant containing a reducing substance of the present invention exhibits a sufficient sterilizing effect even in an aqueous system in which sulfite ions and thiosulfate ions are present. have. Further, 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane can be used as a salt such as a sodium salt and a potassium salt thereof.

[0006] 2,2'-dihydroxy-5,5'- of the present invention
A bactericide using dichlorodiphenylmethane and brominated acetic esters in combination or having both of them has a more excellent bactericidal effect in an aqueous system containing a reducing substance. Two,
Brominated acetates used with 2'-dihydroxy-5,5'-dichlorodiphenylmethane include:
For example, methyl monobromoacetate, ethyl monobromoacetate, phenyl monobromoacetate, methyl dibromoacetate, ethyl dibromoacetate, 1,2-bis (monobromoacetoxy) ethane, 1,2-bis (monobromoacetoxy) propane, 1,2- Bis (monobromoacetoxy) butane, 1,4-bis (monobromoacetoxy) butane, 1,
4-bis (monobromoacetoxy) butene, 1,2-bis (dibromoacetoxy) ethane, 1,2-bis (dibromoacetoxy) propane, 1,2-bis (dibromoacetoxy) butane, 1,4-bis (dibromo) Acetoxy) butane, 1,4-bis (dibromoacetoxy) butene, and the like. 2,2'-dihydroxy-
There is no particular limitation on the ratio of 5,5'-dichlorodiphenylmethane to the brominated acetic acid ester, but those having a weight ratio of 1:20 to 20: 1 can be particularly preferably used. 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and brominated acetates are
Each of these may be added separately to the aqueous system, or a mixture of 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and brominated acetic esters in a predetermined ratio may be used. The disinfectant of the present invention containing 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane, isothiazolin-3-one compound and brominated acetic acid ester has a particularly excellent disinfecting effect in an aqueous system containing a reducing substance. Have.

[0007] Isothiazoline-3- used in the present invention
The on-based compound has the general formula [2]

Embedded image (Wherein, R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, R ² represents a hydrogen atom or a halogen atom, R ³ represents a hydrogen atom or a halogen atom, or R ² R ³ is condensed to form an aromatic ring.)
-Chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-ethyl-3-isothiazolone, 4,5-dichloro-2-octyl-3-isothiazolone, 4,5-benzoisothiazoline-3- ON etc. can be mentioned. In the case of the present invention, 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and isothiazolin-3-one-based compound may be independently added, but 2,2′-dihydroxy-5,5 '-Dichlorodiphenylmethane becomes the host molecule, isothiazoline-3
Since the -one compound can form a clathrate compound as a guest molecule, it is preferably added in the form of a clathrate compound. However, for the purpose of the present invention, it is not always necessary to form a strictly intermolecular compound, and those having a weight ratio of 1:20 to 20: 1 can be suitably used.

[0008] 2,2'-dihydroxy-5,5'- of the present invention
Examples of brominated acetates used in combination with dichlorodiphenylmethane and an isothiazolin-3-one compound include, for example, methyl monobromoacetate, ethyl monobromoacetate, phenyl monobromoacetate, methyl dibromoacetate,
Ethyl dibromoacetate, 1,2-bis (monobromoacetoxy) ethane, 1,2-bis (monobromoacetoxy)
Propane, 1,2-bis (monobromoacetoxy) butane, 1,4-bis (monobromoacetoxy) butane, 1,
4-bis (monobromoacetoxy) butene, 1,2-bis (dibromoacetoxy) ethane, 1,2-bis (dibromoacetoxy) propane, 1,2-bis (dibromoacetoxy) butane, 1,4-bis (dibromo) Acetoxy) butane, 1,4-bis (dibromoacetoxy) butene, and the like. 2,2'-dihydroxy-
5,5'-dichlorodiphenylmethane and isothiazoline
The ratio of the 3-one compound and the brominated acetic acid ester to be used is not particularly limited, but a ratio of the total of the former two and the latter of 1:20 to 20: 1 by weight is particularly preferable. Can be used. The clathrate compound and the brominated acetic acid esters may be separately added to the aqueous system, or the clathrate between 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and the isothiazolin-3-one compound in advance. A compound in which a compound and a brominated acetic acid ester are blended in a fixed ratio can also be used.

The aqueous bactericide containing a reducing substance of the present invention comprises:
A strong bactericidal effect is maintained for a long time in an aqueous system containing a reducing substance such that an ordinary bactericide for aqueous system loses its effect in a short time. Examples of the reducing substance present in the aqueous system include sulfite ions, thiosulfate ions, and hydrogen sulfide. An aqueous system containing 5 ppm or more of these substances can be considered to be a reducing substance-containing aqueous system. Even in an aqueous system containing less than 5 ppm of a reducing substance, the reducing agent-containing aqueous bactericide of the present invention exhibits a strong bactericidal effect, but in an aqueous system containing less than 5 ppm of a reducing substance, a conventional aqueous germicide is used. Almost satisfactory bactericidal effect can be obtained. The method of using the reducing substance-containing aqueous bactericide of the present invention is not particularly limited, but it is preferable to use the active ingredient by dissolving or dispersing it in water or an organic medium. When dispersed in a medium for use, the smaller the particle size is, the more preferable it is. Practically, it is advantageous to use a fine powder passing through 100 mesh. Although there is no particular limitation on the organic medium, for example, alcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and polyglycerin, diethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monobutyl ether, liquid paraffin, xylene, and toluene Alkyl benzenes, castor oil, soybean oil, olive oil, vegetable oils such as rapeseed oil, terpenes such as hinoki oil, and surfactants such as polyoxyethylene alkyl ether. One of these dispersion media may be used, or two or more of them may be used as a mixture.

The amount of the water-based disinfectant containing a reducing substance of the present invention is appropriately selected depending on the kind of the object to be disinfected to which the disinfectant is applied. When used as a control agent, a good bactericidal effect can be obtained by using the reducing agent-containing aqueous bactericide so that the total amount of the active ingredients is 0.1 to 100 g / m ³ . There is no particular limitation on the method of adding the reducing substance-containing aqueous bactericide of the present invention to an aqueous system,
Composition or inclusion compound of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane or 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and isothiazolin-3-one compound and brominated acetate Can be added simultaneously and 2,2'-dihydroxy-
5,5'-Dichlorodiphenylmethane or a composition or clathrate compound of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and an isothiazolin-3-one compound and a brominated acetic acid ester at the same place in an aqueous system. 2,2'-dihydroxy-
5,5'-Dichlorodiphenylmethane or a composition or clathrate compound of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and an isothiazolin-3-one compound and a brominated acetic acid ester in different aqueous locations They can be added separately.

In the aqueous disinfectant containing a reducing substance of the present invention, a stabilizer such as carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, sodium alginate, xanthan gum, or the like may be used, if desired.
Ramzan gum, sodium polyacrylate, polyacrylamide, alkyl methacrylate / diethylaminoethyl methacrylate copolymer, alkyl methacrylate / N-vinyl-2-pyrrolidone copolymer, alkyl methacrylate / polyethylene glycol methacrylate copolymer, dodecyl fumarate / diethylaminoethyl Methacrylate copolymer, styrene / maleic acid copolymer, sodium naphthalene sulfonate-formalin condensate, sodium melamine sulfonate-formalin condensate, sodium lauryl sulfate, sodium lauryl benzene sulfonate, polyoxyethylene alkyl ether, polyalkylene glycol Carbamates,
Alkyl benzene sulfonic acid, nonionic surfactant and the like can be used. The reducing agent-containing aqueous disinfectant of the present invention is not only used as a slime control agent in the paper industry, but is effective for all aqueous compositions containing a reducing agent, for example, starch,
It can be used as a casein preservative, an SBR latex, a preservative for paints and adhesives, and a preservative in a system using metal working oil such as cutting oil. When the water-based disinfectant containing a reducing substance of the present invention is used as these preservatives, it is preferable to select the amount to be added so as to be 1 to 2000 g / m ³ .

[0012]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. In addition, each code | symbol in an Example, a reference example, and a comparative example means the following. Drug A used: 20% by weight of 2,2-dibromo-3-nitrilopropionamide and 80% by weight of diethylene glycol
Mixture. Drug B used: 4,5-dichloro-1,2-dithiol-3
Mixture of 10% by weight of one and 90% by weight of diethylene glycol monomethyl ether. Drug C: 5-chloro-2-methyl-4-isothiazolin-3-one 10% by weight and diethylene glycol 90
Wt% mixture. Drug D: A mixture of 50% by weight of 1,4-bis (bromoacetoxy) -2-butene and 50% by weight of ethylene glycol monomethyl ether. Drug E used: a mixture of 10% by weight of 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane and 90% by weight of diethylene glycol monomethyl ether. Drug F: Inclusion compound of 2,2'-dihydroxy-5,5'-dichlorodiphenylmethane and 5-chloro-2-methyl-4-isothiazolin-3-one (inclusion ratio: about 7:
3) A mixture of 10% by weight and 90% by weight of water.

Example 1, Reference Examples 1 to 3 and Comparative Examples 1 to 8 A sterilizing effect and a growth inhibiting effect of a chemical were examined using a white water sample collected from a white water silo of a medium-sized paper manufacturing machine of a paper mill. No reducing substance added to white water sample, and 50 pp sodium thiosulfate as reducing substance
A total of three test waters to which m and 100 ppm were added were prepared. These test waters were added to a phosphate buffer (1/50).
M), the pH was adjusted to 6.8. The test chemicals shown in Table 1 were added to these test waters so that the active ingredient concentration in the chemicals used became 20 ppm, and the mixture was shaken at 30 ° C. for 30 minutes. Separately, 3
Shaking was performed at 0 ° C. for 30 minutes, and these were used as blank tests. After the completion of the shaking for 30 minutes, the number of bacteria in each test water was measured and compared with the result of the blank test, and the sterilization rate in each test water was determined by the following equation.

(Equation 1) The results are shown in Table 1.

[0014]

[Table 1]

The chemicals used in the comparative examples have a relatively good bactericidal effect with respect to test water to which sodium thiosulfate is not added, and show a bactericidal rate of 85.0 to 99.8%. ing. However, the bactericidal effect of the drug used in the comparative example was significantly reduced with respect to the test water to which sodium thiosulfate was added, and the bactericidal rate was 51.4% at the highest even at the highest, and was 10% or less in most cases. In some cases, the number of bacteria does not change at all with the test water. On the other hand, in Examples using the reducing substance-containing aqueous bactericide of the present invention, not only an excellent bactericidal effect was exhibited for the test water to which sodium thiosulfate was not added, but also sodium thiosulfate was added. Even in the test water, a sterilization rate of 90% or more is always obtained.
Further, when the results of Example 1 and Reference Examples 1 to 3 are examined in detail, 2,2′-dihydroxy-5 is more excellent than Reference Example 1 using 2,2′-dihydroxy-5,5′-dichlorodiphenylmethane. Reference Example 2 using an inclusion compound of 5,5'-dichlorodiphenylmethane and 5-chloro-2-methyl-4-isothiazolin-3-one has a higher bactericidal rate, and furthermore,
It can be seen that Reference Example 3 and Example 1 in which 1,4-bis (bromoacetoxy) -2-butene was used in combination further improved the sterilization rate. Example 2, Reference Examples 4 to 6 and Comparative Examples 9 to 16 Using the test waters prepared in Example 1, Reference Examples 1 to 3 and Comparative Examples 1 to 8, the concentration of the test water was 5%.
Each test water and bouillon medium were mixed. Three of these samples
The number of bacteria was measured every 4 hours while keeping the temperature at 0 ° C., and the time during which the number of bacteria exceeded 10 times the initial value was determined, and this was defined as the growth inhibition time. The results are shown in Table 2.

[0016]

[Table 2]

The chemicals used in the comparative examples have a relatively good growth inhibitory effect against test water to which sodium thiosulfate is not added, and exhibit a growth inhibition time of 12 to 16 hours. . However, against the test water to which sodium thiosulfate was added, the growth inhibitory effect of the drug used in the comparative example was significantly reduced, and the growth inhibition time was all 4 hours or 8 hours. On the other hand, in Examples using the reducing substance-containing aqueous bactericide of the present invention, not only an excellent growth inhibitory effect was exhibited with respect to test water to which sodium thiosulfate was not added, but also sodium thiosulfate was added. The growth inhibition time of 12 hours or 16 hours was always obtained even in the test water. Example 3, Reference Example 7, and Comparative Examples 17 and 18 An actual machine test was performed on a high-quality paper manufacturing machine of a paper mill. During the test period, the amount of reducing substances in the white water varied in the range of 20 to 100 ppm in terms of sodium thiosulfate. The pH was 7.2 and the water temperature was almost constant at 30 ° C. The drug used was added by the following method. Except for Comparative Example 17, the test was continued for 4 days. After 4 days, the machine was stopped, and the amount of deposits (slime) in the system was observed. The method of adding the used drug and the criteria for determining the effect are as follows.

Example 3 Method of adding drug used Example 3: Drug used D was added to Cebuol three times a day every 8 hours, and 100 ppm as an active ingredient of drug was added to influent water.
Was added to the polydisc filter of the white water collecting system for 15 minutes three times a day every 8 hours so that the active ingredient of the drug was 100 ppm with respect to the influent water. Reference Example 7: The active ingredient D was added to Cebuol as an active ingredient of 100 ppm three times a day every eight hours, based on the influent water.
For 15 minutes, and the used drug E was added to the white water recovery system polydisc filter three times a day every 8 hours for 15 minutes so that the active ingredient of the drug was 100 ppm relative to the influent water. Comparative Example 17: The active ingredient D was added to Cebuol as an active ingredient of the active ingredient D three times a day every 8 hours as an active ingredient of the active ingredient.
m and then added to the white water recovery system polydisc filter for 15 minutes so that the active ingredient A becomes 100 ppm as an active ingredient of the influent water three times a day every 8 hours. . Comparative Example 18: Cebuol was dosed with the used drug D three times a day every 8 hours as an active ingredient of the drug in the influent water at 100 pp.
m was added to the polydisc filter of the white water collection system for 15 minutes, and the used drug C was added to the inflow water every 8 hours for 15 minutes so as to be 100 ppm as a drug active ingredient with respect to the inflow water. Judgment Criteria Rank A: There is no dirt in the system and there is no problem. Rank B: Dirt is seen near the dead space and the draft line, but there is no particular problem. Rank C: Stain is conspicuous everywhere in the system,
Can operate somehow. Rank D: Inoperable due to slime trouble. The results are shown in Table 3. The water-based disinfectant containing a reducing substance of Example did not cause any problem even after the test for 4 days, whereas the disinfectant of Comparative Example 17 caused spotting trouble of the product on the third day, and the test was conducted. I had to stop. In addition, spotting troubles occurred on the fourth day even with the disinfectant of Comparative Example 18.

[0019]

[Table 3]

[0020]

EFFECTS OF THE INVENTION By using the reducing agent-containing water-based disinfectant of the present invention, the generation of slime and the decay of the water system can be prevented for a long period of time even in an aqueous system in which a reducing material is present. Can be operated stably, and a decrease in product quality can be prevented. Further, the cost required for slime control and the cost required for preservation can be reduced.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI A01N 43:80 37:02) (58) Investigated field (Int.Cl. ⁶ , DB name) A01N 31/08 A01N 37/02 A01N 43 / 80 102 CAPLUS (STN) REGISTRY (STN) WPIDS (STN)

Claims (3)

(57) [Claims] 1. Sulfite ion, thiosulfate ion or water sulfide
Containing the above aqueous 5 ppm, 2,2'-dihydroxy -5,
5'-dichlorodiphenylmethane and isothiazoline-3
Inclusion compound with -one compound and brominated acetic ester
1:20 to 20: 1 by weight
A method for sterilizing water containing a reducing substance, comprising the steps of : 2. A slime control agent for a papermaking process.
When used in aqueous systems, the total amount of active ingredients is 0.1 to
It is characterized by being added to 100 g / m ^3.
The method for sterilizing water containing a reducing substance according to claim 1 . 3. A method for use in an aqueous system as a preservative,
Add so that the total amount of active ingredients is 1 to 2000 g / m ³
The method for sterilizing water containing a reducing substance according to claim 1, wherein the water is added .